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But‐2‐ene‐1,4‐diamine and But‐2‐ene‐1,4‐diol as Donors for Thermodynamically Favored Transaminase‐ and Alcohol Dehydrogenase‐Catalyzed Processes
Author(s) -
MartínezMontero Lía,
Gotor Vicente,
GotorFernández Vicente,
Lavandera Iván
Publication year - 2016
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201501066
Subject(s) - chemistry , transamination , ene reaction , enantiomeric excess , catalysis , diamine , pyrrole , hexamethylenediamine , amine gas treating , stereoselectivity , alcohol , tetrahydroisoquinoline , medicinal chemistry , diol , organic chemistry , enantioselective synthesis , stereochemistry , enzyme , polyamide
Both cis ‐ and trans ‐but‐2‐ene‐1,4‐diamines have been prepared and efficiently applied as sacrificial cosubstrates in enzymatic transamination reactions. The best results were obtained with the cis ‐diamine. The thermodynamic equilibrium of the stereoselective transamination process is shifted to the amine formation due to tautomerization of 5 H ‐pyrrole into 1 H ‐pyrrole, achieving high conversions (78–99%) and enantiomeric excess (up to >99%) by using a small excess of the amine donor. Furthermore, when the reaction proceeded, a strong coloration was observed due to polymerization of 1 H ‐pyrrole. A structurally related compound, cis ‐but‐2‐ene‐1,4‐diol, has been utilized as cosubstrate in different alcohol dehydrogenase (ADH)‐mediated bioreductions. In this case, high conversions (91–99%) were observed due to a lactonization process. Both strategies are convenient from both synthetic and atom economy points of view in the production of valuable optically active products.